High melt flow propylene impact copolymer and method

ABSTRACT

The present disclosure provides a polymerization process for the production of a high melt flow propylene impact copolymer. The process includes contacting an active propylene-based polymer having a melt flow rate greater than about 100 g/10 min with one or more olefins in a polymerization reactor to form the propylene impact copolymer with a melt flow rate greater than about 60 g/10 min. The production of the high melt flow propylene impact copolymer may occur in one or more polymerization reactors, utilizing standard hydrogen concentration, and no visbreaking.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a national phase entry under 35 U.S.C. §371of International Application No. PCT/US2009/034881 filed Feb. 23, 2009,published Jul. 22, 2010, which is a continuation of U.S. patentapplication Ser. No. 12/390,897 filed Feb. 23, 2009 now U.S. Pat. No.8,067,510, which is a continuation-in-part application of InternationalPatent Application No. PCT/US2008/073882 filed Aug. 21, 2008 whichclaims priority to U.S. Provisional Patent Application No. 60/957,888filed Aug. 24, 2007, the entire contents of which are incorporated byreference herein.

BACKGROUND

The demand for propylene impact copolymers with high melt flow continuesto increase as the need for more sophisticated polymers continues togrow. In-reactor propylene impact copolymers are copolymers produced byway of polymerization, and do not include visbreaking, for example. Itis difficult to produce high melt flow propylene impact copolymersdirectly by polymerization. Conventional polymerization catalyststypically require the use of very high hydrogen concentrations for theformation of a matrix phase polymer with a melt flow greater than themelt flow of the final propylene impact copolymer. In many cases,provision of a high hydrogen concentration is not possible due toreactor operability limits, safety concerns, and/or economicconsiderations.

Desirable is a polymerization process for the production of a high meltflow propylene impact copolymer. Further desired is a process for theproduction of a high melt flow propylene impact copolymer with highimpact strength. Further desired is a process for the production of ahigh melt flow propylene impact copolymer with high impact strength withreduced risk, or no risk, of process disruption.

SUMMARY

The present disclosure provides polymerization processes for theproduction of a propylene impact copolymer with a high melt flow rate.The high melt flow propylene impact copolymer may also have high impactstrength. The present processes are in-reactor processes and do notinclude visbreaking.

In an embodiment, a polymerization process is provided. Thepolymerization process includes gas phase polymerizing, or forming byway of gas phase polymerization, an active propylene-based polymer in afirst polymerization reactor. The active propylene-based polymer has amelt flow rate greater than about 100 g/10 min as measured in accordancewith ASTM D1238-01 (230° C., 2.16 kg). The process includes introducingthe active propylene-based polymer into a second polymerization reactor.In the second reactor, the propylene-based polymer is contacted with atleast one olefin under polymerization conditions. The process furtherincludes forming a propylene impact copolymer having a melt flow rategreater than about 60 g/min.

In an embodiment, the process includes maintaining a H₂/C₃ mole ratio ofless than 0.3 in one, or both, reactors.

In an embodiment, the process includes forming a propylene impactcopolymer having a volatiles content of less than about 65 μg/g.Volatiles content is measured in accordance with VW standard PV3341.

The present disclosure provides another process. In an embodiment, apolymerization process is provided which includes contacting at leastone olefin with an active propylene-based polymer in a polymerizationreactor under polymerization conditions. The active propylene-basedpolymer has a melt flow rate greater than about 100 g/10 min. Theprocess further includes forming a propylene impact copolymer having amelt flow rate greater than about 85 g/10 min.

In an embodiment, the polymerization reactor is a gas phasepolymerization reactor.

In an embodiment, the process includes maintaining a H₂/C₃ mole ratioless than 0.20 in the reactor.

In an embodiment, the process includes forming a propylene impactcopolymer having a volatiles content of less than about 65 μg/g.

The present disclosure provides a composition. In an embodiment, apropylene impact copolymer is provided which includes a propylene-basedpolymer having a melt flow rate greater than about 100 g/10 min and apropylene/ethylene copolymer dispersed within the propylene-basedpolymer. The propylene impact copolymer has an Fc value from about 5 wt% to about 50 wt % and an Ec value from about 20 wt % to about 90 wt %.The propylene impact copolymer has a melt flow rate greater than about60 g/10 min.

An advantage of the present disclosure is the provision of an improvedprocess for the production of propylene impact copolymer and theproduction of high melt flow propylene impact copolymer in particular.

An advantage of the present disclosure is the provision of an improvedpropylene impact copolymer.

An advantage of the present copolymer is the provision of an uncrackedpropylene impact copolymer having high melt flow.

DETAILED DESCRIPTION

In an embodiment, a polymerization process is provided. Thepolymerization process includes gas phase polymerizing (or forming byway of gas phase polymerization) an active propylene-based polymerhaving a melt flow rate (MFR) greater than about 100 g/10 min. MFR ismeasured in accordance with ASTM D1238-01 (230° C., 2.16 kg). The activepropylene-based polymer is formed in a first polymerization reactorunder polymerization (i.e., gas phase polymerization) conditions. Theprocess further includes introducing the active propylene-based polymerinto a second polymerization reactor where the active propylene-basedpolymer is contacted with at least one olefin other than propylene underpolymerization conditions. The process further includes forming apropylene impact copolymer having a melt flow rate greater than about 60g/10 min.

As used herein, an “active polymer” is a polymer containing an amount ofactive catalyst (typically embedded therein) that is capable of furtherpolymerization upon exposure to an olefin under polymerizationconditions. In an embodiment, the active catalyst embedded in the activepropylene-based polymer is a self-limiting catalyst composition whichincludes a procatalyst composition, a cocatalyst, and a mixed externalelectron donor (M-EED). The M-EED includes a first selectivity controlagent (SCA1), a second selectivity control agent, (SCA2) and an activitylimiting agent (ALA). It is understood that the M-EED may include threeor more SCAs and/or two or more ALAs.

The procatalyst composition of the present catalyst composition may be aZiegler-Natta procatalyst composition. Any conventional Ziegler-Nattaprocatalyst may be used in the present catalyst composition. In anembodiment, the Ziegler-Natta procatalyst composition contains atransition metal compound and a Group 2 metal compound. The transitionmetal compound may be a solid complex derived from a transition metalcompound, for example, titanium-, zirconium-, chromium- orvanadium-hydrocarbyloxides, hydrocarbyls, halides, or mixtures thereof.

The transition metal compound has the general formula TrX_(x) where Tris the transition metal, X is a halogen or a C₁₋₁₀ hydrocarboxyl orhydrocarbyl group, and x is the number of such X groups in the compoundin combination with a Group 2 metal compound. Tr may be a Group 4, 5 or6 metal. In an embodiment, Tr is a Group 4 metal, such as titanium. Xmay be chloride, bromide, C₁₋₄ alkoxide or phenoxide, or a mixturethereof. In an embodiment, X is chloride.

Nonlimiting examples of suitable transition metal compounds that may beused to form the Ziegler-Natta procatalyst composition are TiCl₄, ZrCl₄,HfCl₄, TiBr₄, TiCl₃, Ti(OC₂H₅)₃Cl, Zr(OC₂H₅)₃Cl, Ti(OC₂H₅)₃Br,Ti(OC₃H)₂Cl₂, Ti(OC₆H₅)₂Cl₂, Zr(OC₂H₅)₂Cl₂, and Ti(OC₂H₅)Cl₃. Mixturesof such transition metal compounds may be used as well. No restrictionon the number of transition metal compounds is made as long as at leastone transition metal compound is present. In an embodiment, thetransition metal compound is a titanium compound.

Nonlimiting examples of suitable Group 2 metal compounds includemagnesium halides, dialkoxymagnesiums, alkoxymagnesium halides,magnesium oxyhalides, dialkylmagnesiums, magnesium oxide, magnesiumhydroxide, and carboxylates of magnesium. In an embodiment, the Group 2metal compound is magnesium dichloride.

In an embodiment, the Ziegler-Natta procatalyst composition is a mixtureof titanium moieties supported on or otherwise derived from magnesiumcompounds. Suitable magnesium compounds include anhydrous magnesiumchloride, magnesium chloride adducts, magnesium dialkoxides oraryloxides, or carboxylated magnesium dialkoxides or aryloxides. In anembodiment, the magnesium compound is a magnesium di(C₁₋₄)alkoxide, suchas diethoxymagnesium.

Nonlimiting examples of suitable titanium moieties include titaniumalkoxides, titanium aryloxides, and/or titanium halides. Compounds usedto prepare the Ziegler-Natta procatalyst composition include one or moremagnesium-di(C₁₋₄)alkoxides, magnesium dihalides, magnesiumalkoxyhalides, or mixtures thereof and one or more titanium tetra(C₁₋₄)alkoxides, titanium tetrahalides, titanium(C₁₋₄)alkoxyhalides, ormixtures thereof.

A precursor composition may be used to prepare the Ziegler-Nattaprocatalyst composition as is commonly known in art. The precursorcomposition may be prepared by the chlorination of the foregoing mixedmagnesium compounds, titanium compounds, or mixtures thereof, and mayinvolve the use of one or more compounds, referred to as “clippingagents”, that aid in forming or solubilizing specific compositions via asolid/solid metathesis. Nonlimiting examples of suitable clipping agentsinclude trialkylborates, especially triethylborate, phenolic compounds,especially cresol, and silanes.

In an embodiment, the precursor composition is a mixedmagnesium/titanium compound of the formula Mg_(d)Ti(OR_(e))_(f)X_(g)wherein R_(e) is an aliphatic or aromatic hydrocarbon radical having 1to 14 carbon atoms or COR′ wherein R′ is an aliphatic or aromatichydrocarbon radical having 1 to 14 carbon atoms; each OR₃ group is thesame or different; X is independently chlorine, bromine or iodine; d is0.5 to 56, or 2-4; or 3; f is 2-116, or 5-15; and g is 0.5-116, or 1-3,or 2. The precursor may be prepared by controlled precipitation throughremoval of an alcohol from the reaction mixture used in its preparation.In an embodiment, the reaction medium comprises a mixture of an aromaticliquid, especially a chlorinated aromatic compound, such aschlorobenzene, with an alkanol, especially ethanol, and an inorganicchlorinating agent. Suitable inorganic chlorinating agents includechlorine derivatives of silicon, aluminum and titanium, such as titaniumtetrachloride or titanium trichloride, and titanium tetrachloride inparticular. The chlorinating agents lead to partial chlorination whichresults in a precursor containing relatively high level of alkoxycomponent(s). Removal of the alkanol from the solution used in thechlorination, results in precipitation of the solid precursor, having adesirable morphology and surface area. The precursor was separated fromthe reaction media. Moreover, the resulting precursor is particularlyuniform particle sized and resistant to particle crumbling as well asdegradation of the resulting procatalyst. In an embodiment, theprecursor composition is Mg₃Ti(OEt)₈Cl₂.

The precursor is next converted to a solid procatalyst by furtherreaction (halogenation) with an inorganic halide compound, preferably atitanium halide compound, and incorporation of an internal electrondonor. If not already incorporated into the precursor in sufficientquantity, the internal electron donor may be added separately before,during or after halogenation. This procedure may be repeated one or moretimes, optionally in the presence of additional additives or adjuvants,and the final solid product washed with an aliphatic solvent. Any methodof making, recovering and storing the solid procatalyst is suitable foruse in the present disclosure.

One suitable method for halogenation of the precursor is by reacting theprecursor at an elevated temperature with a tetravalent titanium halide,optionally in the presence of a hydrocarbon or halohydrocarbon diluent.The preferred tetravalent titanium halide is titanium tetrachloride. Theoptional hydrocarbon or halohydrocarbon solvent employed in theproduction of olefin polymerization procatalyst preferably contains upto 12 carbon atoms inclusive, or up to 9 carbon atoms inclusive.Exemplary hydrocarbons include pentane, octane, benzene, toluene,xylene, alkylbenzenes, and decahydronaphthalene. Exemplary aliphatichalohydrocarbons include methylene chloride, methylene bromide,chloroform, carbon tetrachloride, 1,2-dibromoethane,1,1,2-trichloroethane, trichlorocyclohexane, dichlorofluoromethane andtetrachlorooctane. Exemplary aromatic halohydrocarbons includechlorobenzene, bromobenzene, dichlorobenzenes and chlorotoluenes. Thealiphatic halohydrocarbon may be a compound containing at least twochloride substituents such as carbon tetrachloride or1,1,2-trichloroethane. The aromatic halohydrocarbon may be chlorobenzeneor o-chlorotoluene.

The halogenation may be repeated one or more times, optionallyaccompanied by washing with an inert liquid such as an aliphatic oraromatic hydrocarbon or halohydrocarbon between halogenations andfollowing halogenation. Further optionally one or more extractionsinvolving contacting with an inert liquid diluent, especially analiphatic or aromatic hydrocarbon, or aliphatic or aromatichalohydrocarbon, especially at an elevated temperature greater than 100°C., or greater than 110° C., may be employed to remove labile species,especially TiCl₄.

In an embodiment, the Ziegler-Natta procatalyst composition includes asolid catalyst component obtained by (i) suspending a dialkoxy magnesiumin an aromatic hydrocarbon or halohydrocarbon that is liquid at normaltemperatures, (ii) contacting the dialkoxy magnesium with a titaniumhalide and further (iii) contacting the resulting composition a secondtime with the titanium halide, and contacting the dialkoxy magnesiumwith a diester of an aromatic dicarboxylic acid at some point during thetreatment with the titanium halide in (ii).

In an embodiment, the Ziegler-Natta procatalyst composition includes asolid catalyst component obtained by (i) suspending a precursor materialof the formula Mg_(d)Ti(OR_(e))_(f)X_(g) (as described previously) in anaromatic hydrocarbon or halohydrocarbon that is liquid at normaltemperatures, (ii) contacting the precursor with a titanium halide andfurther (iii) contacting the resulting composition a second time withthe titanium halide, and contacting the precursor with a diester of anaromatic dicarboxylic acid at some point during the treatment with thetitanium halide in (ii).

The procatalyst composition includes an internal electron donor. As usedherein, an “internal electron donor” is a compound added or otherwiseformed during formation of the procatalyst composition that donates apair of electrons to one or more metals present in the resultantprocatalyst composition. Not bounded by any particular theory, it isbelieved that the internal electron donor assists in regulating theformation of active sites, thereby enhancing catalyst stereoselectivity.

In an embodiment, the internal electron donor is a bidentate compound. A“bidentate compound,” as used herein, is a compound containing at leasttwo oxygen-containing functional groups, the oxygen-containingfunctional groups separated by at least one saturated C₂-C₁₀ hydrocarbonchain which may optionally contain heteroatom(s). The bidentate compoundmay be a phthalate, a diether, a succinate, a phenylene dibenzoate, amaleate, a malonate, a glutarate, a dialkoxybenzene, abis(alkoxyphenyl), a diol ester, a ketoester, an alkoxyalkyl ester, abis(alkoxyalkyl)fluorene, and any combination thereof.

In an embodiment, the internal electron donor is diisobutyl phthalateand/or di-n-butyl phthalate.

In an embodiment, the internal electron donor is9,9-bis(methoxymethyl)-9H-fluorene.

In an embodiment, the internal electron donor is a phenylene dibenzoate.

The Ziegler-Natta procatalyst composition may also include an inertsupport material. The support may be an inert solid which does notadversely alter the catalytic performance of the transition metalcompound. Examples include metal oxides, such as alumina, and metalloidoxides, such as silica.

The present catalyst composition includes a cocatalyst. The cocatalystfor use with the foregoing Ziegler-Natta procatalyst composition may bean aluminum containing composition. Nonlimiting examples of suitablealuminum containing compositions include organoaluminum compounds, suchas trialkylaluminum-, dialkylaluminum hydride-, alkylaluminumdihydride-, dialkylaluminum halide-, alkylaluminumdihalide-,dialkylaluminum alkoxide-, and alkylaluminum dialkoxide-compoundscontaining from 1-10, or 1-6 carbon atoms in each alkyl- oralkoxide-group. In an embodiment, the cocatalyst is a C₁₋₄trialkylaluminum compound, such as triethylaluminum (TEA or TEAl). Themolar ratio of aluminum to titanium is 10-200:1, or 35-50:1. In anembodiment, the molar ratio of aluminum to titanium to 45:1.

The present catalyst composition includes a mixed external electrondonor (M-EED) which includes a first selectivity control agent (SCA1), asecond selectivity control agent (SCA2), and an activity limiting agent(ALA). As used herein, an “external electron donor” (or “EED”) is acompound added independent of procatalyst formation that contains atleast one functional group that is capable of donating a pair ofelectrons to a metal atom. Bounded by no particular theory, it isbelieved that provision of one or more external electron donors in thecatalyst composition affects the following properties of the formantpolymer: level of tacticity (i.e., xylene soluble material), molecularweight (i.e., melt flow), molecular weight distribution (MWD), meltingpoint, and/or oligomer level.

Nonlimiting examples of suitable compounds for the SCA include siliconcompounds, such as alkoxysilanes; ethers and polyethers, such as alkyl-,cycloalkyl-, aryl-, mixed alkyl/aryl-, mixed alkyl/cycloalkyl-, and/ormixed cycloalkyl/aryl-ethers and/or polyethers; esters and polyesters,especially alkyl, cycloalkyl- and/or aryl-esters of monocarboxylic ordicarboxylic acids, such as aromatic monocarboxylic- ordicarboxylic-acids; alkyl- or cycloalkyl-ether or thioether derivativesof such esters or polyesters, such as alkyl ether derivatives of alkylesters or diesters of aromatic monocarboxylic or dicarboxylic acids; andGroup 15 or 16 heteroatom-substituted derivatives of all of theforegoing; and amine compounds, such as cyclic, aliphatic or aromaticamines, more especially pyrrol or pyridine compounds; all of theforegoing SCA's containing from 2 to 60 carbons total and from 1 to 20carbons in any alkyl or alkylene group, 3 to 20 carbons in anycycloalkyl or cycloalkylene group, and 6 to 20 carbons in any aryl orarylene group.

In an embodiment, SCA1 and/or SCA2 is a silane composition having thegeneral formula (I):SiR_(m)(OR′)_(4·m)  (I)

wherein R independently each occurrence is hydrogen or a hydrocarbyl oran amino group, optionally substituted with one or more substituentscontaining one or more Group 14, 15, 16, or 17 heteroatoms. R containsup to 20 atoms not counting hydrogen and halogen R′ is a C₁₋₂₀ alkylgroup, and m is 0, 1, or 2. In an embodiment, R is C₆₋₁₂ aryl, alkyl oraralkyl, C₃₋₁₂ cycloalkyl, C₃₋₁₂ branched alkyl, or C₃₋₁₂ cyclic aminogroup, R′ is C₁₋₄ alkyl, and m is 1 or 2.

In an embodiment, SCA1 is a dimethoxysilane. The dimethoxysilane maycontain at least one secondary alkyl and/or one secondary amino groupdirectly bonded to the silicon atom. Nonlimiting examples of suitabledimethoxysilanes include dicyclopentyldimethoxysilane,methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane,isopropylisobutyldimethoxysilane, diisobutyldimethoxysilane,t-butylisopropyldimethoxysilane, cyclopentylpyrrolidinodimethoxysilane,bis(pyrrolidino)dimethoxysilane,bis(perhydroisoquinolino)dimethoxysilane, and any combination of theforegoing.

In an embodiment, SCA1 is a stiffness-promoting composition. A“stiffness-promoting composition,” as used herein, is a compositionthat, but for operation according to the process conditions of thepresent disclosure, increases or otherwise enhances the stiffness of aresulting polymer under the polymerization conditions of interest.Nonlimiting examples of suitable stiffness-promoting include any of thedimethoxysilanes disclosed above.

In an embodiment, SCA1 is dicyclopentyldimethoxysilane.

In an embodiment, the SCA2 is a silicon compound selected from adiethoxysilane, a triethoxysilane, a tetraethoxysilane, atrimethoxysilane, a dimethoxysilane containing two linear alkyl groups,a dimethoxysilane containing two alkenyl groups, a diether, adialkoxybenzene, and any combination thereof.

Nonlimiting examples of suitable silicon compounds for SCA2 includedimethyldimethoxysilane, vinylmethyldimethoxysilane,n-octylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane,methyldimethoxysilane, 3-chloropropylmethyldimethoxysilane,2-chloroethylmethyldimethoxysilane, allyldimethoxysilane,(3,3,3-trifluoropropyl)methyldimethoxysilane,n-propylmethyldimethoxysilane, chloromethylmethyldimethoxysilane,di-n-octyldimethoxysilane, vinyl(chloromethyl)dimethoxysilane,methylcyclohexyldiethoxysilane, vinylimethyldiethoxysilane,1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane,n-octylmethyldiethoxysilane, octaethoxy-1,3,5-trisilapentane,n-octadecylmethyldiethoxysilane, methacryloxypropylmethyldiethoxysilane,2-hydroxy-4-(3-methyldiethoxysilylpropoxy)diphenylketone,(3-glycidoxypropyl)methyldiethoxysilane, dodecylmethyldiethoxysilane,dimethyldiethoxysilane, diethyldiethoxysilane,1,1-diethoxy-1-silacyclopent-3-ene, chloromethylmethyldiethoxysilane,bis(methyldiethoxysilylpropyl)amine, 3-aminopropylmethyldiethoxysilane,(methacryloxymethyl)methyldiethoxysilane,1,2-bis(methyldiethoxysilyl)ethane, and diisobutyldiethoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane, benzyltriethoxysilane,butenyltriethoxysilane, (triethoxysilyl)cyclohexane,O-(vinyloxybutyl)-N-triethoxysilylpropylcarbamate,10-undecenyltrimethoxysilane, n-(3 trimethoxysilylpropyl)pyrrole,N-[5-(trimethoxysilyl)-2-aza-1-oxopentyl]caprolactam,(3,3,3-trifluoropropyl)trimethoxysilane, triethoxysilylundecanalethylene glycol acetal, (S)—N-triethoxysilylpropyl-O-menthocarbamate,triethoxysilylpropylethylcarbamate,N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole,(3-triethoxysilylpropyl)-t-butylcarbamate, styrylethyltrimethoxysilane,2-(4-pyridylethyl)triethoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane,(S)—N-1-phenylethyl-N′-triethoxysilylpropylurea,(R)—N-1-phenylethyl-N′-triethoxysilylpropylurea,N-phenylaminopropyltrimethoxysilane, N-phenylaminomethyltriethoxysilane,phenethyltrimethoxysilane, pentyltriethoxysilane,n-octyltrimethoxysilane, n-octyltriethoxysilane,7-octenyltrimethoxysilane, S-(octanoyl)mercaptopropyltriethoxysilane,n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane,methyltrimethoxysilane, methyltriethoxysilane,N-methylaminopropyltrimethoxysilane, 3-methoxypropyltrimethoxysilane,methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane,methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane,and O-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate,tetramethoxysilane and/or tetraethoxysilane.

In an embodiment, SCA2 may be methylcyclohexyldiethoxysilane,di-isobutyldiethoxysilane, n-propyltriethoxysilane, tetraethoxysilane,di-n-butyl-dimethoxysilane, benzyltriethoxysilane,but-3-enyltriethoxysilane, 1-(triethoxysilyl)-2-pentene,(triethoxysilyl)cyclohexane, and any combination of the foregoing.

In an embodiment, the SCA2 is selected from a dimethoxysilane containingtwo linear alkyl groups, a dimethoxysilane containing two alkenyl groupsor hydrogen, wherein one or more hydrogen atoms may be substituted by ahalogen, and any combination thereof.

In an embodiment, SCA2 may be a diether, a dimer of a diether, adialkoxybenzene, a dimmer of a dialkoxybenzene, a dialkoxybenzene linkedby a linear hydrocarbon group, and any combination thereof. It is notedthat the diethers for the ALA set forth below apply equally asnonlimiting examples for the SCA2 diether.

In an embodiment, SCA2 is a melt flow-promoting composition. A “meltflow-promoting composition,” as used herein, is a composition that, butfor operation according to the process conditions of the presentdisclosure, increases the melt flow rate of a resulting polymer underthe polymerization conditions of interest. The melt-flow promotingcomposition may be any silane composition suitable as SCA2 as disclosedabove, a diether, an alkoxybenzene, an ester, a ketone, an amide, and/oran amine.

The M-EED includes an activity limiting agent (ALA). An “activitylimiting agent,” as used herein is a material that reduces catalystactivity at elevated temperature, namely in a polymerization reactor atpolymerization, conditions at a temperature greater than about 100° C.Provision of the ALA results in a self-limiting catalyst composition. Asused herein, a “self-limiting” catalyst composition is a catalystcomposition that demonstrates decreased activity at a temperaturegreater than about 100° C. In other words, “self-limiting” is thedecline of catalyst activity when the reaction temperature rises above100° C. compared to the catalyst activity under normal polymerizationconditions with reaction temperature usually below 80° C. In addition,as a practical standard, if a polymerization process, such as afluidized bed, gas-phase polymerization running at normal processingconditions is capable of interruption and resulting collapse of the bedwith reduced risk with respect to agglomeration of polymer particles,the catalyst composition is said to be “self-limiting.”

As a standardized measure of polymerization activity at elevatedtemperatures for use herein, catalyst activities are adjusted tocompensate for different monomer concentrations due to temperature. Forexample, if liquid phase (slurry or solution) polymerization conditionsare used, a correction factor to account for reduced propylenesolubility in the reaction mixture at elevated temperatures is included.That is, the catalyst activity is “normalized” to compensate for thedecreased solubility compared to the lower temperature, especially a 67°C. standard. The “normalized” activity, at temperature T, or A_(T), isdefined as the measured activity or (weight polymer/weight catalyst/hr)at temperature T, multiplied by a concentration correction factor,[P(67)]/[P(T)], where [P(67)] is the propylene concentration at 67° C.and [P(T)] is the propylene concentration at temperature T. The equationfor normalized activity is provided below.

${{Normalized}\mspace{14mu}{Activity}\mspace{14mu}(A)} = {{\cdot \frac{\left\lbrack {P(67)} \right\rbrack}{\left\lbrack {P(T)} \right\rbrack}} \times {Activity}\mspace{14mu}(T)}$

In the equation, the activity at temperature T is multiplied by a ratioof the propylene concentration at 67° C. to the propylene concentrationat temperature T. The resulting normalized activity (A), adjusted forthe decrease in propylene concentration with temperature increase, maybe used for comparison of catalyst activities under varying temperatureconditions. The correction factors are listed below for the conditionsused in the liquid phase polymerization.

67° C. 85° C. 100° C. 115° C. 130° C. 145° C. 1.00 1.42 1.93 2.39 2.983.70

The correction factor assumes that polymerization activity increaseslinearly with propylene concentration under the conditions employed. Thecorrection factor is a function of the solvent or diluent used. Forexample, the correction factors listed above are for a common C₆₋₁₀aliphatic hydrocarbon mixture (Isopar™ E, available from Exxon ChemicalCompany). Under gas phase polymerization conditions, monomer solubilityis normally not a factor and activity is generally uncorrected fortemperature difference. That is, activity and normalized activity arethe same.

The “normalized activity ratio” is defined as A_(T)/A₆₇, where A_(T) isthe activity at temperature T and A₆₇ is the activity at 67° C. Thisvalue can be used as an indicator of activity change as a function oftemperature. For example, an A₁₀₀/A₆₇ equal to 0.30 shows that thecatalyst activity at 100° C. is only 30 percent of the catalyst activityat 67° C. It has been found that at 100° C., an A₁₀₀/A₆₇ ratio of 35% orless yields a catalyst system that is self-extinguishing system.

The ALA may be an aromatic ester or a derivative thereof, an aliphaticester or derivative thereof, a diether, a poly(alkylene glycol) ester,and combinations thereof. Nonlimiting examples of suitable aromaticesters include C₁₋₁₀ alkyl or cycloalkyl esters of aromaticmonocarboxylic acids. Suitable substituted derivatives thereof includecompounds substituted both on the aromatic ring(s) or the ester groupwith one or more substituents containing one or more Group 14, 15 or 16heteroatoms, especially oxygen. Examples of such substituents include(poly)alkylether, cycloalkylether, arylether, aralkylether,alkylthioether, arylthioether, dialkylamine, diarylamine,diaralkylamine, and trialkylsilane groups. The aromatic carboxylic acidester may be a C₁₋₂₀ hydrocarbyl ester of benzoic acid wherein thehydrocarbyl group is unsubstituted or substituted with one or more Group14, 15 or 16 heteroatom containing substituents and C₁₋₂₀(poly)hydrocarbyl ether derivatives thereof, or C₁₋₄ alkyl benzoates andC₁₋₄ ring alkylated derivatives thereof, or methyl benzoate, ethylbenzoate, propyl benzoate, methyl p-methoxybenzoate, methylp-ethoxybenzoate, ethyl p-methoxybenzoate, and ethyl p-ethoxybenzoate.In an embodiment, the aromatic carboxylic acid ester is ethylp-ethoxybenzoate.

In an embodiment, the ALA is an aliphatic ester. The aliphatic ester maybe a C₄-C₃₀ aliphatic acid ester, may be a mono- or a poly- (two ormore) ester, may be straight chain or branched, may be saturated orunsaturated, and any combination thereof. The C₄-C₃₀ aliphatic acidester may also be substituted with one or more Group 14, 15 or 16heteroatom containing substituents. Nonlimiting examples of suitableC₄-C₃₀ aliphatic acid esters include C₁₋₂₀ alkyl esters of aliphaticC₄₋₃₀ monocarboxylic acids, C₁₋₂₀ alkyl esters of aliphatic C₈₋₂₀monocarboxylic acids, C₁₋₄ alkyl mono- and diesters of aliphatic C₄₋₂₀monocarboxylic acids and dicarboxylic acids, C₁₋₄ alkyl esters ofaliphatic C₁₋₂₀ monocarboxylic acids and dicarboxylic acids, and C₄₋₂₀mono- or polycarboxylate derivatives of C₂₋₁₀₀ (poly)glycols or C₂₋₁₀₀(poly)glycol ethers. In a further embodiment, the C₄-C₃₀ aliphatic acidester may be isopropyl myristate and/or di-n-butyl sebacate.

In an embodiment, the ALA is isopropyl myristate.

In an embodiment, the ALA is a diether. The diether may be a dialkyldiether represented by the following formula,

wherein R¹ to R⁴ are independently of one another an alkyl, aryl oraralkyl group having up to 20 carbon atoms, which may optionally containa group 14, 15, 16, or 17 heteroatom, provided that R¹ and R² may be ahydrogen atom. Nonlimiting examples of suitable dialkyl ether compoundsinclude dimethyl ether, diethyl ether, dibutyl ether, methyl ethylether, methyl butyl ether, methyl cyclohexyl ether,2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,2,2-di-n-butyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane,2-ethyl-2-n-butyl-1,3-dimethoxypropane,2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-dimethyl-1,3-diethoxypropane,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2,2-dicyclopentyl-1,3-dimethoxypropane,2-n-propyl-2-cyclohexyl-1,3-diethoxypropane, and9,9-bis(methoxymethyl)fluorene. In a further embodiment, the dialkylether compound is 2,2-diisobutyl-1,3-dimethoxypropane.

In an embodiment, the ALA is a poly(alkylene glycol) ester. Nonlimitingexamples of suitable poly(alkylene glycol) esters include poly(alkyleneglycol) mono- or diacetates, poly(alkylene glycol) mono- ordi-myristates, poly(alkylene glycol) mono- or di-laurates, poly(alkyleneglycol) mono- or di-oleates, glyceryl tri(acetate), glyceryl tri-esterof C₂₋₄₀ aliphatic carboxylic acids, and any combination thereof. In anembodiment, the poly(alkylene glycol) moiety of the poly(alkyleneglycol) ester is a poly(ethylene glycol).

In an embodiment, the molar ratio of aluminum to ALA may be 1.4-85:1, or2.0-50:1, or 4-30:1. For ALA that contains more than one carboxylategroup, all the carboxylate groups are considered effective components.For example, a sebacate molecule contains two carboxylate functionalgroups is considered to have two effective functional molecules.

In an embodiment, the catalyst composition includes a mole ratio of Alto M-EED of 0.5-25:1, or 1.0-20:1, or 1.5-15:1, or less than about 6.0,or less than about 5, or less than 4.5.

In an embodiment, the Al:M-EED mole ratio is 0.5-4.0:1. Not wishing tobe bound by any particular theory, it is believed that the Al/M-EEDratio of 0.5:1 to 4.0:1 provides a sufficient amount of aluminum tosupport the polymerization reaction at normal polymerizationtemperatures. However, at elevated temperature (due to a temperatureexcursion or a process upset, for example), more aluminum species reactwith other catalyst components. This leads to an aluminum deficiencywhich slows the polymerization reaction. The aluminum deficiency causesa corresponding reduction in the number of electron donors complexedwith the aluminum. The free electron pairs of the non-complexed donorspoison the catalyst system, which self-extinguishes the reaction.

As used herein, “total-SCA” is the combined amount (in moles) of SCA1and SCA2. In other words, total-SCA=SCA1(mole)+SCA2 (mole). The amountof ALA in M-EED enhances catalyst self-limiting capability at elevatedtemperature, while the amount of SCA1 provides stiffness and SCA2provides melt flow in the resultant polymer. The total-SCA to ALA moleratio is 0.43-2.33:1, or 0.54-1.85:1, or 0.67-1.5:1. The SCA1 tototal-SCA mole ratio is 0.2-0.5:1, 0.25-0.45:1, or 0.30-0.40:1.Applicants have surprisingly and unexpectedly discovered that acontrolled mole ratio of: (1) SCA1 to SCA2, and/or (2) total-SCA to ALAand/or (3) SCA1 to total-SCA yields a resultant polymer with the uniqueproperties of high melt flow and high stiffness in conjunction with theoperability property of a self-limiting catalyst.

In an embodiment, the mole ratio of total-SCA to ALA is 0.43-2.33:1 andthe mole ratio of SCA1 to total-SCA is 0.2-0.5:1.

In an embodiment, the catalyst composition includes a mole ratio of Alto total-SCA of 1.4-85:1, or 2.0-50:1, or 4.0-30:1.

In an embodiment, the catalyst composition includes a mole ratio oftotal-SCA to ALA that is less than 1.0. Surprisingly and unexpectedly,it has been found that maintaining the mole ratio of total-SCA to ALA toless than 1.0 significantly improves reactor operability.

In an embodiment, the M-EED comprises dicyclopentyldimethoxysilane(SCA1), a melt-flow promoting composition (SCA2), and isopropylmyristate (ALA). In a further embodiment, SCA2 is selected frommethylcyclohexyldiethoxysilane, diisobutyldiethoxysilane,di-n-butyl-dimethoxysilane, n-propyltriethoxysilane,benzyltriethoxysilane, butenyltriethoxysilane,(triethoxysilyl)cyclohexane, tetraethoxysilane,1-ethoxy-2-(6-(2-ethoxyphenoxy)hexyloxy)benzene,1-ethoxy-2-n-pentoxybenzene, and any combination thereof.

The mole ratios between various components of the present catalystcomposition are set forth below in Table 1.

TABLE 1 Mole Ratio Range Al to Ti   10-200:1 Al to M-EED  0.5-25:1 Ti toM-EED    1-100:1 Al to total-SCA  1.4-85:1 Al to ALA  1.4-85:1 total-SCAto ALA   0.43-2.33:1 SCA1 to SCA2   0.1-1.0:1 SCA1 to total-SCA  0.2-0.5:1

The present catalyst composition may comprise two or more embodimentsdisclosed herein.

In an embodiment, the formation of the active propylene-based polymeroccurs by way of a gas phase polymerization process whereby the catalystcomposition is contacted with propylene and optionally one or moreolefins in the first polymerization reactor. One or more olefin monomerscan be optionally introduced into the first polymerization reactor alongwith the propylene to react with the catalyst and to form a polymer, acopolymer, (or a fluidized bed of polymer particles). Nonlimitingexamples of suitable olefin monomers include ethylene, C₄₋₂₀ α-olefins,such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene,1-octene, 1-decene, 1-dodecene and the like; C₄₋₂₀ diolefins, such as1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene(ENB) and dicyclopentadiene; C₈₋₄₀ vinyl aromatic compounds includingstyrene, o-, m-, and p-methylstyrene, divinylbenzene, vinylbiphenyl,vinylnapthalene; and halogen-substituted C₈₋₄₀ vinyl aromatic compoundssuch as chlorostyrene and fluorostyrene.

As used herein, “polymerization conditions” are temperature and pressureparameters within a polymerization reactor suitable for promotingpolymerization between the catalyst composition and an olefin to formthe desired polymer. The polymerization process may be a gas phase, aslurry, or a bulk polymerization process, operating in one, or more thanone, polymerization reactor. Accordingly, the polymerization reactor maybe a gas phase polymerization reactor, a liquid-phase polymerizationreactor, or a combination thereof.

It is understood that provision of hydrogen in the polymerizationreactor is a component of the polymerization conditions. Duringpolymerization, hydrogen is a chain transfer agent and affects themolecular weight (and correspondingly the melt flow rate) of theresultant polymer.

In an embodiment, polymerization occurs by way of gas phasepolymerization. As used herein, “gas phase polymerization,” or “gasphase polymerizing,” is the passage of an ascending fluidizing medium,the fluidizing medium containing one or more monomers, in the presenceof a catalyst through a fluidized bed of polymer particles maintained ina fluidized state by the fluidizing medium. “Fluidization,” “fluidized,”or “fluidizing” is a gas-solid contacting process in which a bed offinely divided polymer particles is lifted and agitated by a risingstream of gas. Fluidization occurs in a bed of particulates when anupward flow of fluid through the interstices of the bed of particlesattains a pressure differential and frictional resistance incrementexceeding particulate weight. Thus, a “fluidized bed” is a plurality ofpolymer particles suspended in a fluidized state by a stream of afluidizing medium. A “fluidizing medium” is one or more olefin gases,optionally a carrier gas (such as H₂ or N₂) and optionally a liquid(such as a hydrocarbon) which ascends through the gas-phase reactor.

A typical gas-phase polymerization reactor (or gas phase reactor)includes a vessel (i.e., the reactor), the fluidized bed, a distributionplate, inlet and outlet piping, a compressor, a cycle gas cooler or heatexchanger, and a product discharge system. The vessel includes areaction zone and a velocity reduction zone, each of which is locatedabove the distribution plate. The bed is located in the reaction zone.In an embodiment, the fluidizing medium includes propylene gas and atleast one other gas such as an olefin and/or a carrier gas such ashydrogen or nitrogen. In an embodiment, the gas phase polymerization isperformed in condensing mode.

In an embodiment, the contacting occurs by way of feeding the catalystcomposition into the polymerization reactor and introducing the olefininto the polymerization reactor. In an embodiment, the process includescontacting the olefin with a cocatalyst. The cocatalyst can be mixedwith the procatalyst composition (pre-mix) prior to the introduction ofthe procatalyst composition into the polymerization reactor. In anotherembodiment, cocatalyst is added to the polymerization reactorindependently of the procatalyst composition. The independentintroduction of the cocatalyst into the polymerization reactor can occursimultaneously, or substantially simultaneously, with the procatalystcomposition feed.

In an embodiment, the process includes mixing or otherwise combining theM-EED with the procatalyst composition. The M-EED can be complexed withthe cocatalyst and/or mixed with the procatalyst composition (pre-mix)prior to contact between the catalyst composition and the propylene. Inanother embodiment, the M-EED (or individual components thereof) may beadded independently to the polymerization reactor.

In an embodiment, the polymerization process includes maintaining ahydrogen-to-propylene (“H₂/C₃”) mole ratio less than 0.30 (i.e.,0.30:1), or less than 0.20, or less than 0.18, or less than 0.16, orless than 0.08 in the first reactor. Although high melt flow can beachieved by using high level of hydrogen, it has been found thatpropylene-based polymers produced by way of a H₂/C₃ mole ratio greaterthan 0.30 significantly accelerate an unwanted reaction of hydrogenationof propylene in the presence of oxidized carbon steel of a reactor andreduce catalyst activity. On the other hand, the resultantpropylene-based polymer formed by way of the present process avoidsexcessive amounts of catalytic residue as the H₂/C₃ mole ratio is lessthan 0.3.

Moreover, a low H₂/C₃ mole ratio value, such as the present value ofless than 0.30, improves catalyst productivity. As the value for theH₂/C₃ mole ratio increases, more hydrogen displaces greater amounts ofpropylene. Hydrogen displacement of propylene decreases the amount ofpropylene available for reaction with the catalyst composition. Thus, alarge value for the H₂/C₃ mole ratio indicates that less propylene isavailable to polymerize. Less propylene available for reactiontranslates into less polymer produced—an indication of decreasedcatalyst activity and decreased reactor productivity.

Conversely, the present catalyst composition enables the formation ofhigh melt flow propylene-based polymer by way of a low H₂/C₃ mole ratio,namely, a H₂/C₃ mole ratio of less than 0.3. Thus, the improved hydrogenresponse of the present catalyst composition improves catalyst activityand improves productivity.

In an embodiment, the polymerization process includes maintaining ahydrogen partial pressure below about 80 psi, or below about 71 psi, orbelow about 63 psi.

In an embodiment, the process includes self-limiting the polymerizationprocess when the temperature in the reactor is greater than about 100°C.

In an embodiment, the process includes forming the propylene-basedpolymer in a single polymerization reactor.

Applicants have surprisingly and unexpectedly discovered that thepresence of the mixed external electron donor provides a catalystcomposition that is self-limiting and produces propylene-based polymerswith high stiffness and high melt flow in a single polymerizationreactor under standard polymerization conditions. Not wishing to bebound by any particular theory, it is believed that the ALA improvesoperability in the polymerization reactor by preventing a run-awayreaction, polymer sheeting, and/or polymer agglomeration caused byexcessive heat. Provision of SCA1 and SCA2 enables the formation of ahigh stiffness (i.e., T_(MF) greater than 170° C.)/high melt flow (i.e.,greater than 50, or 60, or 70, or 100 g/10 min) propylene-based polymerwith utilization of standard hydrogen levels.

In particular, the present process advantageously produces apropylene-based polymer with high stiffness and high melt flow withoutvisbreaking—a conventional technique for increasing the MFR beyond thehydrogen usage limitations of a reactor-grade high stiffnesspropylene-based polymer as described previously. The term “visbreaking”(or “cracking”), as used herein, is the thermal and/or chemicaldegradation of a polymer into smaller polymer chain segments.Visbreaking typically includes placing a polymer (such as polypropylene)in a melt state in the presence of a free radical initiator (such as aperoxide) to degrade the polypropylene into smaller polypropylene chainsegments. Visbreaking is a post-reactor procedure. It is understood thatthe present processes for producing propylene impact copolymer arein-reactor, polymerization processes. Thus the present processes forproducing propylene impact copolymer do not include visbreaking.

Visbreaking has many side effects such as formation of decompositionproducts (which oftentimes cause odor and food incompatibilityproblems), added cost, and a reduction in polymer stiffness. Visbreakingincreases the melt flow yet decreases the weight average molecularweight of a polymer. Visbreaking alters the physical and chemicalstructure of the initial polymer. For example, a visbroken polypropylenehomopolymer will exhibit a reduction in physical and/or mechanicalproperties (i.e. a lower tensile modulus, a lower flexural modulus)compared to an uncracked propylene homopolymer with the same MFR.

In an embodiment, the present process forms an uncracked propylene-basedpolymer. A polymer that is “uncracked” has not been subject to avisbreaking procedure. In other words, an uncracked polymer is anon-thermally and/or non-chemically degraded polymer. An uncrackedpolymer does not exhibit a decline of physical and/or mechanicalproperties related to molecular weight (such as flexural modulus and/ortensile properties), as does a visbroken polymer at the same MFR. Inaddition, an uncracked polymer does not experience decompositionproducts (which oftentimes cause odor and food incompatibility problems)as does a visbroken polymer.

In an embodiment, the process includes forming a propylene-based polymerhaving one or more of the following properties: (i) an uncrackedpropylene homopolymer; (ii) a MFR greater than 50 g/10 min, or greaterthan 60 g/10 min, or greater than 70 g/10 min, or greater than 100 g/10min; (iii) a xylene solubles content of less than 4 wt %. or less than3% wt %, or from about 0.1 wt % to less than 2.0 wt %; (iv) a T_(MF)greater than about 165° C., or greater than 170° C.; (v) an ALA contentof at least about 5 ppm to about 150 ppm; (vi) a post-reactor oligomercontent (“oligomers” are C₁₂-C₂₁ compounds) less than 3000 ppm, or lessthan 2500 ppm, or from about 500 ppm to about 3000 ppm; and/or (vii) apost-reactor oligomer content about 10%, or about 20%, or about 40% lessthan the corresponding oligomer content of a propylene-based polymerformed by a catalyst composition which contains a singlestiffness-promoting composition SCA (and optionally an ALA) undersimilar polymerization conditions. The term “post-reactor oligomercontent,” as used herein, is the oligomer content of the resultantpropylene-based polymer immediately after exit from the polymerizationreactor. In other words, “post-reactor oligomer content” is the oligomercontent prior to any post-polymerization washing procedure, heatingprocedure, and/or refining procedure.

In an embodiment, the uncracked propylene-based polymer is a propylenehomopolymer. In a further embodiment, the propylene-based polymer haslow or no toxicity, low or no decomposition products, and low or nounpleasant odor.

In an embodiment, the active propylene-based polymer may be produced asdisclosed in copending application Ser. No. 12/390,897, filed on Feb.23, 2009, the entire content of which is incorporated by referenceherein.

The present process includes introducing the active propylene-basedpolymer into a second polymerization reactor. In an embodiment, thefirst polymerization reactor and the second polymerization reactoroperate in series, whereby the effluent from the first polymerizationreactor is charged to the second polymerization reactor and one or moreadditional (or different) olefin monomer(s) is/are added to the secondpolymerization reactor to continue polymerization. In anotherembodiment, each of the first polymerization reactor and the secondpolymerization reactor is a gas phase polymerization reactor.

The process includes contacting the active propylene-based polymer withat least one olefin in the second polymerization reactor underpolymerization conditions, and forming a propylene impact copolymerhaving a melt flow rate greater than about 60 g/10 min as measured inaccordance with ASTM D1238-01. The at least one olefin includes anolefin other than propylene.

In an embodiment, the process includes forming an active propylene-basedpolymer with a MFR greater than 160 g/10 min and forming a propyleneimpact copolymer with a MFR greater than about 85 g/10 min. In anotherembodiment, the process includes forming an active propylene-basedpolymer with a MFR greater than 200 g/10 min and forming a propyleneimpact copolymer with an MFR greater than about 100 g/10 min. In anotherembodiment, the process includes forming an active propylene-basedpolymer with a MFR greater than about 300 g/10 min and forming apropylene impact copolymer with a MFR greater than about 150 g/10 min.

Propylene impact copolymer is a heterophasic copolymer. As used herein,a “heterophasic copolymer” is a multiple phase polymer having acontinuous polymer phase (also referred to as the matrix phase) and adiscontinuous polymer phase (also referred to as the elastomeric phaseor the rubber phase, or rubber) dispersed within the continuous polymerphase. The propylene-based polymer produced in the first reactor is thecontinuous phase. The olefin is polymerized in the presence of thepropylene-based polymer in the second reactor and forms thediscontinuous phase. A heterophasic copolymer may contain more than twopolymer phases.

The olefin introduced in the second reactor may be propylene, ethylene,a C₄₋₂₀ α-olefin (such as 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene and thelike), or any combination thereof. In an embodiment, propylene andethylene are contacted with the active propylene-based polymer in thesecond reactor to form a propylene impact copolymer with apropylene/ethylene copolymer as the discontinuous phase.

In an embodiment, the propylene impact copolymer has an Fc value fromabout 5 wt % to about 50 wt %, or from about 10 wt % to about 40 wt %,or from about 20 wt % to about 30 wt %. As used herein, “fractioncopolymer” (“Fc”) is the weight percent of the discontinuous phasepresent in the heterophasic copolymer. The Fc value is based on thetotal weight of the propylene impact copolymer.

The propylene impact copolymer may have an Ec value from about 20% wt toabout 90 wt %, or from about 30 wt % to about 80 wt %, or from about 40wt % about 60 wt %. As used herein, “ethylene content” (“Ec”) is theweight percent of ethylene present in the discontinuous phase of thepropylene impact copolymer. The Ec value is based on the total weight ofthe discontinuous (or rubber) phase.

In an embodiment, the polymerization process includes maintaining ahydrogen-to-propylene (“H₂/C₃”) mole ratio less than 0.3 in the firstpolymerization reactor, and/or in the second polymerization reactor. Ithas been found that propylene-based polymers produced by way of a H₂/C₃mole ratio greater than 0.3 contain excessive amounts of catalyticresidue such as titanium and/or chlorine. The resultant propylene-basedpolymer formed by way of the present process avoids excessive amounts ofcatalytic residue as the H₂/C₃ mole ratio is less than 0.3.

In a further embodiment, the process includes maintaining a H₂/C₃ moleratio of less than 0.10, or less than 0.08, or less than 0.04, or lessthan 0.03, in the second polymerization reactor. Applicants havesurprisingly and unexpectedly discovered that maintaining the H₂/C₃ moleratio to less than 0.3 (and/or maintaining the H₂/C₃ mole ratio to lessthan 0.1 in the second reactor) lowers hydrogen consumption and improvescatalyst activity as a smaller presence of hydrogen lowers the partialpressure of the propylene and/or other olefin.

Not bounded by any particular theory, it is believed that the catalystcomposition of the present process contributes to the low level ofvolatiles content of the resultant propylene impact copolymer. In anembodiment, the process includes forming a propylene impact copolymerhaving a volatiles content of less than about 65 μg/g. As used herein,“volatiles” are carbon-containing substances that are driven off asvapor at room temperature or slightly elevated temperatures, from apolymer. The volatiles content is less than about 65 μg/g, or less thanabout 60 μg/g, or less than about 50 μg/g, or from about 10 μg/g to lessthan about 65 μg/g. The volatiles content is determined in accordancewith Volkswagen (VW) standard PV-3341.

The low amount of volatiles content of the present propylene impactcopolymer advantageously reduces, or eliminates, a subsequent purgeprocedure. Conventional propylene impact copolymers typically require anitrogen purge and/or a steam purge (for several days) in order toreduce the volatiles content to acceptable levels—particularly forapplications requiring low volatiles content, such as food containerapplications. The low volatiles content of the present propylene impactcopolymer decreases purge time or eliminates a purge procedurealtogether.

In an embodiment, the process includes self-limiting the polymerizationreaction when the temperature is greater than 100° C. in the firstpolymerization reactor and/or the second polymerization reactor. Notwishing to be bound by any particular theory, it is believed that theALA improves operability in the polymerization reactor by preventing arun-away reaction, polymer sheeting, and/or polymer agglomeration causedby excessive heat formed during polymerization in either reactor.

In an embodiment, the process includes introducing, M-EED, or one ormore components thereof, into the second reactor. Thus, the firstselectivity control agent (SCA1), the second selectivity control agent(SCA2), and/or the activity limiting agent (ALA), separately, or in anycombination, may be added to the second reactor.

The process may comprise two or more embodiments disclosed herein.

The present disclosure provides another process. In an embodiment, apolymerization process is provided which includes contacting, in apolymerization reactor under polymerization conditions, at least oneolefin with an active propylene-based polymer. The activepropylene-based polymer has a melt flow rate greater than about 100 g/10min.

The process further includes forming a propylene impact copolymer havinga melt flow rate of at least 85 g/10 min as measured in accordance withASTM D-1238-01 (230° C., 2.16 kg weight). In an embodiment, thepropylene-based polymer has a MFR greater than about 150 g/10 min andthe propylene impact copolymer has a MFR greater than about 100 g/10min. In another embodiment, the propylene-based polymer has a MFRgreater than about 200 g/0 min and the propylene impact copolymer has aMFR greater than about 150 g/10 min.

In an embodiment, the polymerization occurs by way of gas phasepolymerization. In other words, the contact between the activepropylene-based polymer and the olefin(s) occurs in a gas phasepolymerization reactor under polymerization conditions. Thepolymerization reactor may be the second polymerization reactor asdisclosed above.

In an embodiment, the process includes maintaining a H₂/C₃ mole ratio ofless than 0.20, or less than 0.10, or less than 0.08, or less than 0.04,or less than 0.03 during formation of the propylene impact copolymer.

In an embodiment, the process includes self-limiting the polymerizationwith a catalyst composition embedded in the active propylene-basedpolymer when the temperature in the polymerization reactor is greaterthan about 100° C. The catalyst embedded in the active propylene-basedpolymer may be the catalyst composition disclosed herein having aprocatalyst, a cocatalyst and a mixed external electron donor (M-EED)comprising a first selectivity control agent (SCA1), a secondselectivity control agent (SCA2), and an activity limiting agent (ALA).

In an embodiment, the process includes introducing, M-EED, or one ormore components thereof, into the reactor. Thus, the first selectivitycontrol agent (SCA1), the second selectivity control agent (SCA2),and/or the activity limiting agent (ALA), separately, or in anycombination, may be added to the polymerization reactor.

In an embodiment, the active propylene-based polymer is contacted withpropylene and ethylene. The process includes forming a propylene impactcopolymer with an Fc value from about 5 wt % to about 50 wt %, and an Ecvalue from about 20 wt % to about 90 wt %.

In an embodiment, the process includes melt blending a nucleating agentwith the propylene impact copolymer and forming a nucleated propyleneimpact copolymer. As used herein, “melt blending” is a process in whicha polymer is softened and/or melted and mixed with one or more othercompounds. Nonlimiting examples of melt blending processes includeextrusion, melt mixing (batch or continuous), reactive melt blending,and/or compounding.

The nucleating agent reduces the size of crystallites, thereby improvingthe transparency and clarity of articles made from the propylene impactcopolymer. Not wishing to be bound by any particular theory, it isbelieved that the nucleating agent provides sites for more ordered andfaster polyolefin crystallization during cooling. During the process ofcrystallization, polymer crystals organize into larger superstructureswhich are referred to as spherulites. The spherulites are more uniformand are smaller in size than spherulites formed in the absence of thenucleating agent.

Various nucleating agents known in the art may be used withoutlimitation. Nonlimiting examples of suitable nucleating agents includesodium benzoate, aluminum adipate; aluminum p-t-butylbenzoate; sorbitolacetal derivatives such as 1,3,2,4-dibenzylidenesorbitol,1,3,2,4-bis(p-methyl-benzylidene)sorbitol,1,3,2,4-bis(p-ethylbenzylidene)-sorbitol,1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene-sorbitol,1,3-O-2,4-bis(3,4-dimethylbenzylidene)sorbitol, (available from MillikenChemical Spartanburg, S.C. under the trade name Millad® 3988),1,3-O-2,4-bis(p-methylbenzylidene)sorbitol (also available from MillikenChemical under the trade name Millad® 3940); sodiumbis(4-t-butylphenyl)phosphate; sodium bis(4-t-methylphenyl)phosphate;potassium bis(4,6-di-t-butylphenyl)phosphate; sodium2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate (NA-11); sodium2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate; talc; calciumcarbonate; and any combination of the foregoing.

In an embodiment, the process includes forming a propylene impactcopolymer having a volatiles content of less than about 65 μg/g. Thevolatiles content is less than about 65 μg/g, or less than about 60μg/g, or less than 50 μg/g, or from about 10 μg/g to less than about 65μg/g.

The process may comprise two or more embodiments disclosed herein.

The present disclosure provides a propylene impact copolymer. Thepropylene impact copolymer includes a propylene-based polymer (matrixphase) with a propylene/ethylene copolymer (discontinuous phase)dispersed therein. The propylene-based polymer has a MFR greater thanabout 100 g/10 min. The propylene impact copolymer has a melt flow rategreater than about 60 g/10 min, an Fe value from about 5 wt % to about50 wt %, an Ec value from about 20 wt % to about 90 wt %.

In an embodiment, the propylene-based polymer has a MFR greater thanabout 160 g/10 min and the propylene impact copolymer has a MFR greaterthan about 85 g/10 min. In another embodiment, the propylene-basedpolymer has a MFR greater than about 200 g/10 min and the propyleneimpact copolymer has a MFR greater than about 100 g/10 min. In anembodiment, the propylene-based polymer has a MFR greater than about 300g/10 min and the propylene impact copolymer has a MFR greater than about150 g/10 min. In a further embodiment, the propylene-based polymer is apropylene homopolymer.

In an embodiment, the propylene-based polymer has one or more of thefollowing properties: xylene solubles content of less than about 4 wt %,or less than about 2 wt %; and a T_(MF) greater than about 170° C.

In an embodiment, no polymer component of the propylene impact copolymeris cracked. In other words, the propylene impact copolymer is uncracked,the propylene-based polymer is uncracked, and the propylene/ethylenecopolymer is uncracked.

In an embodiment, the propylene impact copolymer has a volatiles contentof less than 65 μg/g, or less than about 60 μg/g, or less than 50 μg/g,or from about 10 g/g to less than about 65 μg/g (VW PV3341).

In an embodiment, the propylene impact copolymer has an ALA content ofat least 5 ppm, or at least 10 ppm, or at least 20, ppm, or at least 30ppm, or from about 5 ppm to about 150 ppm.

In an embodiment, the propylene impact copolymer is a nucleatedpropylene impact copolymer.

The present propylene impact copolymer may be used for a variety ofapplications such as automotive interior parts where low volatiles arerequired, and can be used for many food contact applications such ascups and containers. Additionally, many ordinary molded articles such astoys, pails, buckets, and general purpose articles can take advantage ofthe high melt flow product and impact strength properties and/or lowvolatiles content of the present propylene impact copolymer. The presentpropylene impact copolymer can also be used to produce fibers forcarpets, upholstery, and diapers.

The propylene impact copolymer may comprise two or more embodimentsdisclosed herein.

Definitions

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Groups or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference),especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

The term “comprising,” and derivatives thereof, is not intended toexclude the presence of any additional component, step or procedure,whether or not the same is disclosed herein. In order to avoid anydoubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compoundwhether polymeric or otherwise, unless stated to the contrary. Incontrast, the term, “consisting essentially of” excludes from the scopeof any succeeding recitation any other component, step or procedure,excepting those that are not essential to operability. The term“consisting of” excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

Any numerical range recited herein, includes all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent, or a value of a compositional or a physical property, suchas, for example, amount of a blend component, softening temperature,melt index, etc., is between 1 and 100, it is intended that allindividual values, such as, 1, 2, 3, etc., and all subranges, such as, 1to 20, 55 to 70, 197 to 100, etc., are expressly enumerated in thisspecification. For values which are less than one, one unit isconsidered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These areonly examples of what is specifically intended, and all possiblecombinations of numerical values between the lowest value and thehighest value enumerated, are to be considered to be expressly stated inthis application. In other words, any numerical range recited hereinincludes any value or subrange within the stated range. Numerical rangeshave been recited, as discussed herein, reference melt index, melt flowrate, and other properties.

The terms “blend” or “polymer blend,” as used herein, is a blend of twoor more polymers. Such a blend may or may not be miscible (not phaseseparated at molecular level). Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and other methods known in the art.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “polymer” is a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike.

The term “interpolymer,” as used herein, refers to polymers prepared bythe polymerization of at least two different types of monomers. Thegeneric term interpolymer thus includes copolymers, usually employed torefer to polymers prepared from two different monomers, and polymersprepared from more than two different types of monomers.

The term “olefin-based polymer” is a polymer containing, in polymerizedform, a majority weight percent of an olefin, for example ethylene orpropylene, based on the total weight of the polymer. Nonlimitingexamples of olefin-based polymers include ethylene-based polymers andpropylene-based polymers.

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized ethylene monomer(based on the total weight of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term, “ethylene/α-olefin interpolymer,” as used herein, refers to aninterpolymer that comprises a majority weight percent polymerizedethylene monomer (based on the total amount of polymerizable monomers),and at least one polymerized α-olefin.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized propylene monomer(based on the total amount of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term “alkyl,” as used herein, refers to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Nonlimitingexamples of suitable alkyl radicals include, for example, methyl, ethyl,n-propyl, i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl,i-butyl (or 2-methylpropyl), etc. The alkyls have 1 and 20 carbon atoms.

The term “substituted alkyl,” as used herein, refers to an alkyl as justdescribed in which one or more hydrogen atom bound to any carbon of thealkyl is replaced by another group such as a halogen, aryl, substitutedaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halogen, haloalkyl, hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

The term “aryl,” as used herein, refers to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. The aryls have 1 and20 carbon atoms.

Test Methods

Flexural modulus is determined in accordance with ASTM D790-00 Method I,using an ASTM D 638 Type 1 specimen tested at 1.3 mm/min.

Izod impact strength is measured in accordance with ASTM D256.

Melt flow rate (MFR) is measured in accordance with ASTM D 1238-01 testmethod at 230° C. with a 2.16 kg weight for propylene-based polymers.

Xylene Solubles (XS) is measured according to the following procedure.0.4 g of polymer is dissolved in 20 ml of xylenes with stirring at 130°C. for 30 minutes. The solution is then cooled to 25° C. and after 30minutes the insoluble polymer fraction is filtered off. The resultingfiltrate is analyzed by Flow Injection Polymer Analysis using a ViscotekViscoGEL H-100-3078 column with THF mobile phase flowing at 1.0 ml/min.The column is coupled to a Viscotek Model 302 Triple Detector Array,with light scattering, viscometer and refractometer detectors operatingat 45° C. Instrument calibration was maintained with Viscotek PolyCAL™polystyrene standards.

Final melting point T_(MF) is the temperature to melt the most perfectcrystal in the sample and is regarded as a measure for isotacticity andinherent polymer crystallizability. The test is conducted using a TAQ100 Differential Scanning Calorimeter. A sample is heated from 0° C. to240° C. at a rate of 80° C./min, cooled at the same rate to 0° C., thenheated again at the same rate up to 150° C., held at 150° C. for 5minutes and the heated from 150° C. to 180° C. at 1.25° C./min. TheT_(MF) is determined from this last cycle by calculating the onset ofthe baseline at the end of the heating curve.

Testing Procedure:

-   -   (1) Calibrate instrument with high purity indium as standard.    -   (2) Purge the instrument head/cell with a constant 50 ml/min        flow rate of nitrogen constantly.

(3) Sample preparation:

-   -   Compression mold 1.5 g of powder sample using a 30-G302H-18-CX.        Wabash Compression Molder (30 ton): (a) heat mixture at 230° C.        for 2 minutes at contact; (b) compress the sample at the same        temperature with 20 ton pressure for 1 minute; (c) cool the        sample to 45° F. and hold for 2 minutes with 20 ton        pressure; (d) cut the plaque into 4 of about the same size,        stack them together, and repeat steps (a)-(c) in order to        homogenize sample.

(4) Weigh a piece of sample (preferably between 5 to 8 mg) from thesample plaque and seal it in a standard aluminum sample pan. Place thescaled pan containing the sample on the sample side of the instrumenthead/cell and place an empty sealed pan in the reference side. If usingthe auto sampler, weigh out several different sample specimens and setup the machine for a sequence.

(5) Measurements:

-   -   (i) Data storage: off    -   (ii) Ramp 80.00° C./min to 240.00° C.    -   (iii) Isothermal for 1.00 min    -   (iv) Ramp 80.00° C./min to 0.00° C.    -   (v) Isothermal for 1.00 min    -   (vi) Ramp 80.00° C./min to 150.00° C.    -   (vii) Isothermal for 5.00 min    -   (viii) Data storage: on    -   (ix) Ramp 1.25° C./min to 180.00° C.    -   (x) End of method

(6) Calculation: T_(MF) is determined by the interception of two lines.Draw one line from the base-line of high temperature. Draw another linefrom through the deflection of the curve close to the end of the curveat high temperature side.

Volatiles content—is measured by the static Headspace Analysis describedin the textbook: Pyrolysis and GC in Polymer Analysis, edited by S. A.Liebman and E. J. Levy, Marcel Dekker, Inc., 1985. The gaschromatography/head-space gas chromatography (GC-HS) analysis is widelyused in the automotive industry. The company Volkswagen AG has developeda standard, which is generally accepted and used in the plasticindustry. It is known as “VW standard PV 3341” (or “PV3341”). PV 3341 isa test in which a sample of 2 grams is placed into a headspace vial,conditioned for 5 hours at 120° C. and then injected into a GC.Quantification is accomplished using an external standard techniquebased on peak area response of acetone standards.

By way of example and not by limitation, examples of the presentdisclosure will now be provided.

EXAMPLES (1) Procatalysts

SHAC 320 is a Ziegler-Natta procatalyst composition composed oftitanium, magnesium, and an internal electron donor ofdi-isobutylphthalate and prepared according to example 1 in U.S. Pat.No. 6,825,146, the entire content of which is incorporated by referenceherein.

Procatalyst FV is a Ziegler-Natta procatalyst composition composed oftitanium, magnesium, and an internal electron donor of a 1,3-diether asdisclosed in European Patent Application No. 728,769. The FV procatalystis prepared as follows.

At ambient temperature, 350 g of a mixed magnesium/titanium halidealcoholate, 72 g of 9,9-bis(methoxymethyl)-9H-fluorene, and 5.6 L of a50/50 (vol/vol) mixture of titanium(IV) chloride and chlorobenzene arecombined. The mixture is agitated at 105-115° C. for 60 min, allow tosettle, and filtered at 100° C. The solids are agitated in 2.8 L ofchlorobenzene at 85° C., allowed to settle, and filtered at 85° C. Thesolids are twice stirred in 5.6 L of a fresh mixture of 50/50titanium(IV) chloride and chlorobenzene at 105-115° C. for 30 min, isallowed to settle, and is filtered at 100° C. After cooling, the solidsare washed twice with 5.2 L of hexane at 50-60° C., followed by a finalwash with 5.6 L of 2-methylbutane at ambient temperature. The solids arecombined with 1.19 kg of mineral oil, and the resulting slurry wassubjected to vacuum to remove residual volatiles.

(2) External Electron Donors

Samples A-E include a mixed external electron donor (M-EED) with theM-EED components selected from the following:

DCPDMS: dicyclopentyldimethoxysilane (SCA)

IPM: isopropyl myristate (ALA)

PTES: n-propyltriethoxysilane (SCA2)

TEOS: tetraethoxysilane (SCA2)

Sample F includes an external electron donor with components selectedfrom the following.

DCPDMS: dicyclopentyldimethoxysilane (SCA)

IPM: isopropyl myristate (ALA)

Samples G and H are conventional impact copolymers. Sample H is preparedwith a catalyst composition which includes dicyclopentyldimethoxysilaneas the external electron donor. Samples G and H are provided ascomparisons and are not embodiments of the present disclosure.

(3) Polymerization

Production of the samples A-F and sample H is performed in the gas phaseusing linked fluidized bed reactors such as described in U.S. Pat. No.4,882,380, the entire content of which is incorporated by referenceherein. Polymerization conditions are those listed in Table 2 below.

Sample G is a conventional impact copolymer that is made in a Spheripolprocess, a known multi-stage process using a liquid phase polymerizationreactor in the first stage, followed by one or two additional gas phasepolymerization reactors for the production of the rubber phase. Thefinished grade is a reactor grade (i.e., not visbroken).

As a final step in the production of samples A-F, each sample issemi-continuously discharged into a fiberpak and sparged (ordeactivated) with wet nitrogen at 22° C., using approximately 3 kg ofwater per 1000 kg of resin for a period up to 3 hours.

After resin from sample H is discharged from the reactor, it isdeactivated by purging for 1-3 hours with wet nitrogen at 22° C., using1 kg of water per 1000 kg of polymer.

Samples A-F and H are compounded with the additives listed in Table 4using twin screw, intermeshing extruders. No purging is done on thesesamples following the compounding.

TABLE 2 A B C D E F G* H* Catalyst SHAC SHAC SHAC SHAC SHAC SHAC 320 320320 320 320 FV 320 Rx 1 Conditions Rx 1 H₂/C₃ 0.144 0.15 0.177 0.1880.192 0.075 0.178 Rx Temp (C.) 70 70 70 70 70 70 65 Molar 21.0 13.3 21.013.3 13.3 4.3 1 Al/DCPDMS Molar 8.0 na 8.0 8.0 na na Al/TEOSMolar/Al/PTES 7.0 na 7.0 na na na na Molar/Al/IPM 3.5 3.3 3.5 3.3 3.32.8 na Rx 1 Al/SCA 2.1 2 2.1 2 2 1.7 1 Rx 1 Al/Ti 49 49 49 49 49 49 40Propylene 2208 2208 2208 2208 2202 2622 partial pressure (kPa) Rx 1residence 2.7 2.9 3.1 3 2.9 3.3 1.3 time (hours) MFR 139.0 153.0 210.0195.0 205.0 187.0 61 (homopolymer) dg/min XS 1.7 1.6 2.3 1.7 1.8 1.8 1.6(homopolymer) wt % RX 2 Conditions Rx 2 Temp (C.) 70 70 70 70 70 70 70Rx 2 Propylene 95 78 93 88 81 82 41 partial pressure (psi) Rx 2residence 2 2.1 2.1 2 2 2 1 time (hours) Rx 2 H₂/C₃ 0.023 0.022 0.0230.022 0.021 0.017 0.096 Volatiles 47.7 55.6 58.45 46.9 70.4 125 Content(μg/g) Pellet Product Properties MFR (g/10 78 74 80 90 108 82 82 33 min)Ec (% wt) 44.5 45.2 43.4 44.3 44.5 43.4 49.3 52 Fc (% wt) 17.3 16.9 18.518.2 17.3 18.4 18.9 17 Non-nucleated ISO Flex 173,455 176,146 162,116169,689 170,574 157,451 Chord (psi) ISO Flex 1,197 1,215 1,119 1,1711,177 1,086 Chord (MPa) ISO Notched 7.63 8.39 9.73 9.47 8.4 9.85 Izod@23 C. (KJ/M²) ISO Charpy at 7.21 7.85 8.42 8.31 7.83 9.2 23° C. (KJ/M²)*= Comparative

TABLE 3 A B C D E F G* H* Nucleated with 1000 ppmw NA-11 ISO Flex221,093 221,552 210,400 218,637 197,370 Chord (psi) 1,526 1,529 1,4521,509 1,362 ISO Notched 7.49 7.81 8.08 7.02 10 Izod @23 C. (KJ/M²) ISOCharpy at 7.21 7.63 8.27 6.59 10 23° C. (KJ/M²) Nucleated with 500 ppmwNaBz ISO Flex 1,380 1,396 1,413 1493** Chord (MPa) ISO Notched 7.14 8.037.4    8.3** Izod @23 C. (KJ/M²) ISO Charpy at 7.4 7.4 6.8 23° C.(KJ/M²) ASTM 1% 1539  secant flex modulus (MPa) ASTM RT 76 Izod (J/m) *=Comparative **= Values calculated based on a correlation to the ASTMvalues listed in the table

TABLE 4 Additives (ppmw) Examples A-G Irganox 1010 (hindered phenolicantioxidant) 1000 Irgafos 168 (Phosphite Antioxidant) 1000 GMS (glycerolmonostearate) 6000 Calcium Stearate (acid acceptor) 600 If nucleatedwith NA-11 NA-11—nucleating agent 1000 If nucleated with NaBz CalciumStearate 0 Zinc Oxide (acid acceptor) 200 NaBz (Sodium Benzoate) 500Example H Irganox 1010 750 P-EPQ—Phosphite Antioxidant 750 Acrawax CLubricant 500 DHT-4A Zeolite Acid Acceptor 250 NaBz 500

Samples A-F have a lower volatiles content than comparative Sample H inspite of the fact that Samples A-F each have a higher MFR than Sample H.

Sample F shows that by using a different catalyst (FV catalyst) incombination with IPM and DCPDMS the same result can be achieved, namely,the production of a propylene impact copolymer with high melt flow and alow volatiles content. Furthermore, by using IPM in combination withDCPDMS (and optionally the other silanes) a lower amount of DCPDMS isneeded, providing a further cost reduction since the DCPDMS is morecostly.

Samples A and B each has the same, or substantially the same, impact andstiffness properties as Sample G (using substantially the same, or thesame, additives). Surprisingly and unexpectedly, the present propyleneimpact copolymer produced in the gas phase is superior in volatilescontent. In particular, samples A and B each have a smaller volatilescontent than sample G.

It is specifically intended that the present invention not be limited tothe embodiments and illustrations contained herein, but include modifiedforms of those embodiments including portions of the embodiments andcombinations of elements of different embodiments as come within thescope of the following claims.

The invention claimed is:
 1. A polymerization process comprising:contacting propylene and optionally at least one other olefin with acatalyst composition in a first polymerization reactor under gas phasepolymerization conditions, the catalyst composition comprising aprocatalyst having a diether internal electron donor which is9,9-bis(methoxymethyl)-9H-fluorene, a cocatalyst and a mixed externalelectron donor (M-EED) comprising a first selectivity control agent(SCA1) which is dicyclopentyldimethoxysilane and an activity limitingagent (ALA) which is isopropyl myristate; forming, in the firstpolymerization reactor, an active propylene-based polymer having a meltflow rate greater than 100 g/10 min as measured in accordance with ASTMD1238-01 (230° C., 2.16 kg); contacting the active propylene-basedpolymer with at least one olefin in a second reactor underpolymerization conditions; and forming a propylene impact copolymerhaving a melt flow rate greater than 60 g/10 min and an Izod impactstrength of 9.85 kJ/m².
 2. The process of claim 1 comprising maintaininga H₂/C₃ mole ratio of less than 0.3 in one or both reactors.
 3. Theprocess of claim 1 comprising maintaining a H₂/C₃ mole ratio of lessthan 0.1 in the second polymerization reactor.
 4. The process of claim 1comprising introducing into the second reactor, a component selectedfrom the group consisting of a mixed external electron donor (M-EED), afirst selectivity control agent (SCA1), a second selectivity controlagent (SCA2), an activity limiting agent (ALA), and combinationsthereof.
 5. The process of claim 1 comprising contacting the activepropylene-based polymer with propylene and ethylene and forming apropylene impact copolymer having an Fc value from about 5 wt % to about50 wt % and an Ec value from about 20 wt % to about 90 wt %.
 6. Theprocess of claim 1 comprising forming a propylene impact copolymerhaving a volatiles content of less than 65 μg/g as measured inaccordance with VW standard PV3341.
 7. The process of claim 1 comprisingself-limiting the polymerization with the catalyst composition when thetemperature is greater than 100° C. in a reactor selected from the groupconsisting of the first polymerization reactor, the secondpolymerization reactor, and combinations thereof.
 8. A polymerizationprocess comprising: contacting, in a polymerization reactor underpolymerization conditions, at least one olefin with an activepropylene-based polymer having a melt flow rate greater than 100 g/10min as measured in accordance with ASTM D-1238-01 (230° C., 2.16 kg) anda catalyst composition comprising a procatalyst having a dietherinternal electron donor which is 9,9-bis(methoxymethyl)-9H-fluorene andan activity limiting agent (ALA) which is isopropyl myristate; andforming a propylene impact copolymer having a melt flow rate greaterthan 85 g/10 min, an Izod impact strength of 9.85 kJ/m², and at least 5ppm of the ALA.
 9. The process of claim 8 comprising contacting the atleast one olefin with the active propylene-based polymer in a gas phasepolymerization reactor.
 10. The process of claim 8 comprisingmaintaining a H₂/C₃ mole ratio of less than 0.2.
 11. The process ofclaim 8 wherein the active propylene-based polymer comprises aself-limiting catalyst composition, the process comprising self-limitingthe polymerization when the temperature in the polymerization reactor isgreater than 100° C.
 12. The process of claim 8 comprising contactingpropylene and ethylene with the active propylene-based polymer; andforming a propylene impact copolymer having an Fc value from about 5 wt% to about 50 wt % and an Ec value from about 20 wt % to about 90 wt %.13. The process of claim 8 comprising forming a propylene impactcopolymer having a volatiles content of less than 65 μg/g as measured inaccordance with VW standard PV3341.
 14. A propylene impact copolymercomprising: a propylene-based polymer having a melt flow rate (MFR)greater than 100 g/10 min as measured in accordance with ASTM D-1238-01(230° C., 2.16 kg); a propylene/ethylene copolymer dispersed within thepropylene-based polymer, and the propylene impact copolymer having amelt flow rate greater than 60 g/10 min, an Fc value from about 5 wt %to about 50 wt %, an Ec value from about 20 wt % to about 90 wt %, anIzod impact strength of 9.85 kJ/m² and at least 5 ppm of an activitylimiting agent (ALA) which is isopropyl myristate.
 15. The propyleneimpact copolymer of claim 14 wherein the MFR of the propylene-basedpolymer is greater than 160 g/10 min and the MFR of the impact copolymeris greater than 85 g/10 min.
 16. The propylene impact copolymer of claim14 wherein the propylene-based polymer has a xylene solubles contentless than 4%.
 17. The propylene impact copolymer of claim 14 wherein thepropylene-based polymer is uncracked.
 18. The propylene impact copolymerof claim 14 comprising a volatiles content of less than 65 μg/g asmeasured in accordance with VW standard PV3341.
 19. The propylene impactcopolymer of claim 14 having a T_(mf) greater than 170° C.